[go: up one dir, main page]

US4556553A - Toothpaste composition - Google Patents

Toothpaste composition Download PDF

Info

Publication number
US4556553A
US4556553A US06/499,447 US49944783A US4556553A US 4556553 A US4556553 A US 4556553A US 49944783 A US49944783 A US 49944783A US 4556553 A US4556553 A US 4556553A
Authority
US
United States
Prior art keywords
toothpaste composition
composition according
toothpaste
aluminum oxide
plastics
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US06/499,447
Inventor
Nobuo Suganuma
Kensuke Tanaka
Nobuyuki Takada
Hiromichi Ichikawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lion Corp
Original Assignee
Lion Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lion Corp filed Critical Lion Corp
Assigned to LION CORPORATION reassignment LION CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ICHIKAWA, HIROMICHI, SUGANUMA, NOBUO, TAKADA, NOBUYUKI, TANAKA, KENSUKE
Application granted granted Critical
Publication of US4556553A publication Critical patent/US4556553A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/345—Alcohols containing more than one hydroxy group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26—Aluminium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/731—Cellulose; Quaternized cellulose derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
    • B65D35/02—Body construction
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/87—Application Devices; Containers; Packaging

Definitions

  • This invention relates to toothpaste compositions with which plastics containers having oxygen permeability of 3 cc/m 2 ⁇ day ⁇ atm or more are filled. More particularly, this invention relates to toothpaste compositions which exhibit increased antiseptic properties when received in plastics containers including plastics tubes, aluminum foil-plastics coating laminate tubes and plastics bottles.
  • toothpaste compositions are contained in suitable containers and squeezed out of the containers onto a toothbrush immediately before they are used. It is therefore required that such toothpaste is kept hygienically acceptable in the container, easily extruded through a container opening, easily applied onto a tooth brush, and retains its shape on the toothbrush.
  • Commonly used toothpaste containers are generally classified into two groups: metal containers including aluminium tubes and plastic containers including plastics tubes formed solely of plastics material, laminate tubes comprising an aluminium foil coated with a plastics layer on an inner or each surface and formed into a tube, and plastic bottles.
  • metal containers including aluminium tubes
  • plastic containers including plastics tubes formed solely of plastics material
  • laminate tubes comprising an aluminium foil coated with a plastics layer on an inner or each surface and formed into a tube
  • plastic bottles Such a plastics bottle has a wall of substantial thickness and can restore its shape immediately after the pressure applied to squeeze a desired amount of toothpaste out of the bottle is released.
  • the plastics bottle has an aesthetic appearance and can stand on its cap, requiring a minimum space.
  • metal containers especially aluminum tubes are susceptible to corrosion or pitting. This problem may be overcome by modifying the formulation of toothpaste compositions or by replacing aluminum tubes by plastics containers.
  • plastics containers including plastic tubes, plastics bottles, and laminate tubes comprising an aluminum foil coated with a plastics layer on an inner or each surface.
  • plastics containers capable of more or less restoring their shape immediately after the pressure applied to squeeze a desired amount of toothpaste out of the container is released allow aerobic bacteria to grow or propagate easily in their contents or toothpaste as compared with aluminum tubes.
  • plastics containers having oxygen permeability of 3 cc/m 2 ⁇ day ⁇ atm or more are filled with toothpaste compositions, aerobic bacteria would grow or propagate very easily.
  • toothpaste compositions should be more antiseptic when plastic containers, particularly those containers with a high restoring force are used.
  • toothpastes are rendered antiseptic by incorporating antiseptics and bactericides therein.
  • some bactericides for example, quarternary ammonium salt bactericides have been reported as coloring tooth enamel.
  • the use of such antiseptics and bactericides is strictly limited by Governmental regulations. Since toothpaste compositions are destined for oral application, it is desired for increased hygienic safety that the amount of antiseptics and bactericides blended is as small as possible.
  • an object of the present invention to provide an improved toothpaste composition which exhibits increased antiseptic properties with a minimum amount of an antiseptic and/or bactericide when filled in a plastics container having oxygen permeability of 3 cc/m 2 ⁇ day ⁇ atm or more.
  • Toothpaste compositions to which the present invention is directed are to be received in plastics containers including plastics bottles, plastics tubes and aluminum foil-plastic coating laminate tubes.
  • the plastics containers have oxygen permeability of 3 cc/m 2 ⁇ day ⁇ atm or more.
  • the toothpaste composition comprises an aluminum oxide compound as a main abrasive and a polyhydric alcohol.
  • the polyhydric alcohol is blended in an amount of 5.0 to 100 moles per liter of water in the toothpaste composition when the composition is free of any fluoride.
  • the polyhydric alcohol is blended in an amount of 4.0 to 100 moles per liter of water in the toothpaste composition when the composition contains a fluoride.
  • the toothpaste compositions of the present invention which contain an aluminum oxide compound as a main abrasive and a polyhydric alcohol in an amount of 5.0 to 100 moles in fluoride-free systems or 4.0 to 100 moles in fluoride-containing systems per liter of water in the toothpaste compositions have high antiseptic power against aerobic bacteria although the toothpastes compositions are filled in plastics containers having oxygen permeability of 3 cc/m 2 ⁇ day ⁇ atm or more which allow aerobic bacteria to grow or propagate very easily.
  • the use of a polyhydric alcohol in the above-defined contents in combination with an aluminum oxide abrasive renders the toothpaste compositions highly antiseptic.
  • the toothpaste compositions of the present invention are effective to suppress the growth of aerobic bacteria, they may be advantageously stored in plastics containers having a high restoring force for a long period of time without a change in quality.
  • an antiseptic and/or bactericide may be blended in a minimum amount so that the toothpaste compositions of the present invention are highly safe for oral application.
  • FIGS. 1 to 3 are partially broken away side views of plastics containers filled with the composition of the present invention, respectively.
  • FIG. 4 is a graph showing the relationship between numbers of surviving bacilli and storage period when toothpaste compositions are filled in various containers.
  • the toothpaste composition of this invention comprises an aluminium oxide compound as a main abrasive and a polyhydric alcohol.
  • aluminas and hydrated aluminas are known including ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ and ⁇ types classified in terms of crystal systems and physical properties. Among them ⁇ -alumina and hydrated ⁇ -alumina are preferred because of high stability.
  • the hydrated aluminas which can be used herein are gibbsite and bayerite (represented by Al 2 O 3 .3H 2 O, respectively), boehmite and diaspore (represented by Al 2 O 3 .H 2 O, respectively) and the like.
  • hydrated aluminas are preferred in view of abrasiveness, tooth abrasion and the like.
  • Alumina trihydrates having the formula:
  • the preferred alumina trihydrate is gibbsite which is commercially available.
  • the aluminum oxide compounds may be used alone or in admixture of two or more.
  • the aluminum oxide compound should be in the form of particles having an average particle size of 1-50 microns, preferably 3-25 microns when measured by the sedimentation method.
  • the aluminum oxide compound is blended in an amount of 10 to 70% by weight, preferably 30 to 60% by weight of the total weight of the toothpaste composition although the exact blending amount may vary with a particular type of the toothpaste composition.
  • the toothpaste composition of this invention may further include other additional abrasives, for example, dicalcium phosphate dihydrate and anhydride, calcium carbonate, calcium pyrophosphate, silica, aluminum silicate, insoluble sodium metaphosphate, magnesium tertiary phosphate, magnesium carbonate, synthetic resins and other known abrasives alone or in admixture generally in an amount of less than about 10% by weight in terms of the weight of the aluminium oxide compound.
  • additional abrasives for example, dicalcium phosphate dihydrate and anhydride, calcium carbonate, calcium pyrophosphate, silica, aluminum silicate, insoluble sodium metaphosphate, magnesium tertiary phosphate, magnesium carbonate, synthetic resins and other known abrasives alone or in admixture generally in an amount of less than about 10% by weight in terms of the weight of the aluminium oxide compound.
  • the polyhydric alcohols which can be used in the present invention include ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycerine, sorbitol, xylitol, maltitol, lactitol, etc. and mixtures thereof.
  • Amounts of the polyhydric alcohols blended fall within the range of 5.0 to 100 moles in fluoride-free systems or within the range of 4.0 to 100 moles in fluoride-containing systems per liter of water in the toothpaste compositions.
  • the presence of polyhydric alcohols in the above-defined ranges is effective to preclude aerobic bacteria from growing or propagating in plastics containers, providing highly antiseptic toothpaste compositions.
  • the upper limit of the molar number of a polyhydric alcohol is 100 moles, preferably 50 moles for reasons of toothpaste feeling and cost. More strictly, the upper limit is 15 moles when the smoothness and stringiness of toothpaste upon extrusion are taken into account.
  • a fluoride may preferably be blended in the toothpaste composition in addition to the polyhydric alcohol.
  • the fluoride is effective to further improve the antiseptic properties of the toothpaste composition and to lower the lower limit of the amount of the polyhydric alcohols blended as understood from the above-defined ranges.
  • the fluorides are stannous fluoride, sodium fluoride, and alkali metal monofluorophosphates such as sodium monofluorophosphate, and potassium monofluorophosphate, with the monofluorophosphates being preferred.
  • the fluoride compounds such as alkali metal monofluorophosphates, when blended in an amount of 0.1 to 1% by weight of the total weight of the toothpaste composition, ensure satisfactory antiseptic action and tooth enamel reinforcement.
  • the toothpaste composition of the present invention may further contain as a binder an alkali metal salt of carboxymethyl cellulose such as sodium carboxymethyl cellulose because of the effectiveness to enhance the antiseptic properties of the toothpaste composition.
  • the alkali metal salts of carboxymethyl cellulose may preferably be those having an average degree of etherification of 0.75 to 0.90 because these salts are effective for shape retention of the toothpaste composition. With degrees of etherification of lower than 0.75, the toothpaste compositions become too hard so that an extrudate of toothpaste will readily tumble down from a toothbrush when applied onto the toothbrush.
  • the carboxymethyl cellulose salts may preferably be blended in an amount of 0.2 to 5%, particularly 0.5 to 2% by weight of the total weight of the toothpaste composition.
  • the toothpaste composition of the present invention may further contain other additives well know in the art.
  • additives include anionic and nonionic surface active agents.
  • the anionic surface active agents may include water-soluble salts of the higher alkyl sulfates having 8 to 18 carbon atoms in the alkyl group (e.g., sodium lauryl sulfate and sodium mirystyl sulfate), water-soluble salts of sulfonated monoglycerides of higher fatty acids having 10 to 18 carbon atoms in the fatty acid group (e.g.
  • the nonionic surface active agents may include alkyrol diethanol amides (e.g. lauroyl diethanol amide), stearyl monoglyceride, sucrose fatty acid esters having 12 to 18 carbon atoms in the fatty acid group (e.g.
  • the toothpaste composition may also contain amphoteric surface active agents such as those of betaine and amino acid types, etc. These surface active agents may be blended alone or in admixture in an amount of 0.2 to 7% by weight of the composition.
  • flavors such as spearming oil and peppermint oil (in an amount of 0.1 to 3% by weight), clove oil, cassia oil, sage oil, coriander oil, anise oil, wintergreen oil, eucalyptus oil, and fruit flavors (in an amount of 0.001 to 1% by weight).
  • a natural essential oil may be partially replaced by a synthetic or isolated flavor, for example, l-menthol, anethole, carvone, eugenol, etc.
  • sweeteners such as sodium saccharin, stevioside, neohesperidin dihydrocalcone, glycyrrhizin, perillartine, p-methoxycinnamic aldehyde, etc. may be blended.
  • the toothpaste composition of the present invention may contain humectants other than polyhydric alcohols as well as binders other than alkali metal salts of carboxymethyl cellulose.
  • the other binders include carrageenan, alkali metal alginates such as sodium alginate, gums such as xanthan gum, synthetic binding agents such as polyvinyl alcohol, inorganic binding agents such as silica gel, veegum, aluminum silicate gel, etc. and mixtures thereof.
  • the other binders may be blended alone or in admixture, preferably in admixture with alkali metal salts of carboxymethyl cellulose in an amount of 0 to 2% by weight of the composition.
  • the toothpaste composition of this invention may further include other active ingredients, for example, enzymes such as amylase, protease, mutanase, lysozyme, lytic enzyme, etc., stannous compounds, ⁇ -aminocaproic acid, tranexamic acid, aluminum chlorohydroxyallantoinate, dihydrocholesterol, glycyrrhetinates, glycerophosphate, sodium chloride, water-soluble inorganic phosphates, and the like alone or in admixture.
  • the watersoluble inorganic phosphate are potassium and sodium salts of orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid, while the potassium salts are preferred.
  • antiseptics such as ethyl p-hydroxybenzoate and butyl p-hydroxybenzoate
  • bactericides such as bacterial quarternary ammonium salts and chlorhexidine and its salts may be blended in an amount of 0 to 0.5% by weight of the composition.
  • the toothpaste composition of the present invention may be prepared by selecting the necessary ingredients from the above-mentioned ingredients and kneading them with water.
  • the toothpaste composition according to this invention may generally have a pH or 4.5 to 10, preferably 6 to 8.5.
  • FIG. 1 shows one example of a collapsable plastics tube.
  • the tube 10 has a tubular body 12 which consists of a plastics material inner layer 14 and a plastic material outer layer 16, a shoulder 18, and a cap 20.
  • FIG. 2 shows one example of a collapsable laminate tube.
  • the tube 24 has a tubular body 26 which consists of a plastics material inner layer 28, an aluminum foil intermediate layer 30 and a plastics material outer surface 32, a shoulder 34, and a cap 36.
  • FIG. 3 shows one example of a plastic bottle.
  • the bottle 40 has a bottle body 42 which consists of a plastic material single layer 44, and a cap 46.
  • numerals 22, 38 and 48 designate a toothpaste composition packed in the containers 10, 24 and 40.
  • the number of the layer(s) is not limited to the above Figures.
  • the body of the plastics container may have a single layer or multiple layers.
  • Plastic material of the plastic containers may be selected from ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyvinyl chloride, nylon, polyester, polyethylene, polypropylene, etc.
  • the toothpaste composition of the present invention is advantageously and safely stored in the plastics container having oxygen permeability of 3 cc/m 2 ⁇ day ⁇ atm or more for a long period of time without a change in quality because they are effective to prevent aerobic bacteria from growing or propagating. More detailedly, a plastics container having oxgen permeability of 3 cc/m 2 ⁇ day ⁇ atm or more would allow aerobic bacteria to grow or propagate very easily in its content or toothpaste compositions. However, when the toothpaste compositions according to the present invention are filled in the plastic container having oxgen permeability of 3 cc/m 2 ⁇ day ⁇ atm or more, aerobic bacteria are effectively prevented from growing or propagating because the antiseptic properties of the toothpaste composition according to the present invention are very high.
  • Toothpaste compositions having the formulation shown below were prepared in a conventional manner.
  • Tube A Laminate tube having an epoxy resin inner layer of 20 ⁇ m thick, an aluminum foil intermediate layer of 10 ⁇ m thick and a low-density polyethylene outer layer of 100 ⁇ m thick.
  • the shoulder portion of the tube A consists of a polyethylene single layer.
  • Tube B Laminate tube having an epbxy resin inner layer of 20 ⁇ m thick, an aluminum foil intermediate layer of 15 ⁇ m thick and a low-density polyethylene outer layer of 100 ⁇ m thick.
  • the shoulder portion of the tube B consists of a polyethylene single layer.
  • Tube C Laminate tube having an epoxy resin inner layer of 20 ⁇ m thick, an aluminum foil intermediate layer of 20 ⁇ m thick and a low-density polyethylene outer layer of 100 ⁇ m thick.
  • the shoulder portion of the tube C consists of inner and outer layers of polyethylene and an intermediate layer of aluminum foil.
  • Tube D Laminate tube having an epoxy resin inner layer of 20 ⁇ m thick, an aluminum foil intermediate layer of 20 ⁇ m thick and a low-density polyethylene outer layer of 100 ⁇ m thick.
  • the shoulder portion of the tube D consists of an inner layer of urea resin and an outer layer of polyethylene.
  • Tube E Plastics tube having an ethylene-vinyl acetate copolymer inner layer (vinyl acetate content 10%) of 200 ⁇ m thick, an ethylenevinyl alcohol intermediate layer of 50 ⁇ m thick and an ethylene-vinyl acetate copolymer inner layer of 250 ⁇ m thick.
  • Tube F Plastics tube having a single layer of 500 ⁇ m which consists of a mixture of 100 parts by weight of a blend of 20% of a low-density polyethylene (density 0.917) with 80% of a saponified ethylene-vinyl acetate copolymer (ethylene content 76%, degree of saponification 93%) and 5 parts by weight of a polyamide having a carbonyl concentration of 1.6 meq./g.
  • Tube G Plastics tube having an inner layer of 350 ⁇ m thick which consists of a blend of 55% of a low-density polyethylene (density 0.917) with 45% of a saponified ethylene-vinyl acetate copolymer (ethylene content 76%, degree of saponification 93%) and an outer layer of 150 ⁇ m thick which consists of a polyamide having a carbonyl concentration of 1.6 meq./g.
  • Tube H Aluminum tube
  • Oxygen permeability (cc/m 2 ⁇ day ⁇ atm) of the tubes A-H was measured by the following method. The results are shown in Table 1.
  • a tube to be measured is evacuated and purged with nitrogen gas, closed at its opening with a rubber plug, and sealed at the interface between the tube opening and the plug with an epoxy adhesive.
  • the tube is then kept for a given period of time in a temperature and humidity-controlled chamber at a temperature of 37° C. and a relative humidity of 15%.
  • the concentration of oxygen which has permeated through the tube wall into the tube interior is measured by gas chromatography, and the oxygen permeability QO 2 is calculated according to the following equation: ##EQU1## Where m is the volume in ml of nitrogen gas with which the tube is filled, t is the time in day for which the tube is kept in the chamber, Ct is the concentration in vol. % of oxygen in the tube after t days, A is the effective surface area in m 2 of the tube, and Op is the partial pressure of oxygen gas which is equal to 0.209 atm. The result is an average of three tube samples.
  • the toothpaste samples filled in the above tubes were tested for antiseptic properties by the following method.
  • Gram-negative bacillus was isolated from the environment and stored in a slant.
  • a trypticase soy plateoculture medium was smeared with the bacillus.
  • the toothpaste samples were inoculated with the above-prepared bacillus suspension to a concentration of 10 6 -10 7 bacillus/g of toothpaste and thoroughly kneaded.
  • Laminate tubes formed of an aluminum foil coated with a polyethylene film on each surface were filled with the contaminated toothpaste samples and stored at 30° C. The number of surviving bacilli in the toothpaste samples was determined after 1, 2 and 4 weeks. The results are shown in FIG. 4.
  • the evaluation standard is as follows.
  • the toothpaste compositions filled in the plastics containers having oxygen permability of 3 cc/m 2 ⁇ day ⁇ atm or more are not antiseptic.
  • plastics containers having oxygen permeability of 3 cc/m 2 ⁇ day ⁇ atm or more allow aerobic bacteria to grow or propagate very easily as compared with the other tubes having oxygen permeability of less than 3 cc/m 2 ⁇ day ⁇ atm.
  • Aluminum tubes and laminate tubes formed of an aluminum foil having a polyethylene coating on each surface were filled with toothpaste sample Nos. 1 to 6. After being stored at room temperature and 50° C. for one month, the samples were measured for stability. All the toothpaste samples themselves were found to be satisfactorily stable. However, corrosion and blister were observed in those aluminum tubes filled with toothpaste sample Nos. 4 to 6 containing alumina trihydrate abrasive. No problem occurred in the laminate tubes filled with the same samples. Neither the aluminum tubes nor the laminate tubes gave rise to any problem when they were filled with toothpaste sample Nos. 1 to 3 containing dicalcium phosphate abrasive.
  • a plastics tube having oxygen permeability of 25 cc/m 2 ⁇ day ⁇ atm was filled with the above composition.
  • a plastics tube having oxygen permeability of 8 cc/m 2 ⁇ day ⁇ atm was filled with the above composition.
  • a laminate tube formed of an aluminum foil having a plastics coating on each surface was filled with the above composition.
  • the laminate tube had oxygen permeability of 5 cc/m 2 ⁇ day ⁇ atm.
  • the flavor used in the above composition was a mixture of the following components:
  • a plastics tube having oxygen permeability of 120 cc/m 2 ⁇ day ⁇ atm was filled with the above composition.
  • a plastic tube having oxygen permeability of 72 cc/m 2 ⁇ day ⁇ atm was filled with the above composition.
  • a laminate tube formed of an aluminum foil having a plastics coating on each surface was filled with the above composition.
  • the laminate tube had oxygen permeability of 9 cc/m 2 ⁇ day ⁇ atm.
  • a laminate tube formed of an aluminum foil having a plastics coating on each surface was filled with the above composition.
  • the laminate tube had oxygen permeability of 12 cc/m 2 ⁇ day ⁇ atm.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Emergency Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Cosmetics (AREA)

Abstract

A plastics container having oxygen permeability of 3 cc/m2.day.atm or more is filled with an antiseptic toothpaste composition comprising an aluminum oxide compound such as aluminum oxide trihydrate as a main abrasive and a polyhydric alcohol such as propylene glycol, sorbitol, etc. in an amount of 5 to 100 moles in fluoride-free systems or 4.0 to 100 moles in fluoride-containing systems per liter of water in the toothpaste composition.

Description

This application is a continuation-in-part of copending application Ser., No. 316,400 filed on Oct. 29, 1981.
BACKGROUND OF THE INVENTION
This invention relates to toothpaste compositions with which plastics containers having oxygen permeability of 3 cc/m2 ·day·atm or more are filled. More particularly, this invention relates to toothpaste compositions which exhibit increased antiseptic properties when received in plastics containers including plastics tubes, aluminum foil-plastics coating laminate tubes and plastics bottles.
In general, toothpaste compositions are contained in suitable containers and squeezed out of the containers onto a toothbrush immediately before they are used. It is therefore required that such toothpaste is kept hygienically acceptable in the container, easily extruded through a container opening, easily applied onto a tooth brush, and retains its shape on the toothbrush.
Commonly used toothpaste containers are generally classified into two groups: metal containers including aluminium tubes and plastic containers including plastics tubes formed solely of plastics material, laminate tubes comprising an aluminium foil coated with a plastics layer on an inner or each surface and formed into a tube, and plastic bottles. Such a plastics bottle has a wall of substantial thickness and can restore its shape immediately after the pressure applied to squeeze a desired amount of toothpaste out of the bottle is released. The plastics bottle has an aesthetic appearance and can stand on its cap, requiring a minimum space.
Among these containers, as a result of the interaction of a container with its contents or toothpaste composition, metal containers, especially aluminum tubes are susceptible to corrosion or pitting. This problem may be overcome by modifying the formulation of toothpaste compositions or by replacing aluminum tubes by plastics containers.
Concerning plastics containers, no substantial problem has heretofore been found when toothpaste compositions are received in plastics containers including plastic tubes, plastics bottles, and laminate tubes comprising an aluminum foil coated with a plastics layer on an inner or each surface. However, the inventors have experimentally discovered that if contaminants are accidentally introduced into a toothpaste container from the environment, plastics containers capable of more or less restoring their shape immediately after the pressure applied to squeeze a desired amount of toothpaste out of the container is released allow aerobic bacteria to grow or propagate easily in their contents or toothpaste as compared with aluminum tubes. Particularly when plastics containers having oxygen permeability of 3 cc/m2 ·day·atm or more are filled with toothpaste compositions, aerobic bacteria would grow or propagate very easily. Although aerobic bacteria are not pathogenic, the presence of such bacteria in a substantial quantity would have undesired influence on the flavor and stability of toothpaste compositions. It has been thus found that toothpaste compositions should be more antiseptic when plastic containers, particularly those containers with a high restoring force are used.
In general, conventional toothpastes are rendered antiseptic by incorporating antiseptics and bactericides therein. However, some bactericides, for example, quarternary ammonium salt bactericides have been reported as coloring tooth enamel. In addition, the use of such antiseptics and bactericides is strictly limited by Governmental regulations. Since toothpaste compositions are destined for oral application, it is desired for increased hygienic safety that the amount of antiseptics and bactericides blended is as small as possible.
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide an improved toothpaste composition which exhibits increased antiseptic properties with a minimum amount of an antiseptic and/or bactericide when filled in a plastics container having oxygen permeability of 3 cc/m2 ·day·atm or more.
Toothpaste compositions to which the present invention is directed are to be received in plastics containers including plastics bottles, plastics tubes and aluminum foil-plastic coating laminate tubes. The plastics containers have oxygen permeability of 3 cc/m2 ·day·atm or more. According to the present invention, the toothpaste composition comprises an aluminum oxide compound as a main abrasive and a polyhydric alcohol. The polyhydric alcohol is blended in an amount of 5.0 to 100 moles per liter of water in the toothpaste composition when the composition is free of any fluoride. The polyhydric alcohol is blended in an amount of 4.0 to 100 moles per liter of water in the toothpaste composition when the composition contains a fluoride.
The toothpaste compositions of the present invention which contain an aluminum oxide compound as a main abrasive and a polyhydric alcohol in an amount of 5.0 to 100 moles in fluoride-free systems or 4.0 to 100 moles in fluoride-containing systems per liter of water in the toothpaste compositions have high antiseptic power against aerobic bacteria although the toothpastes compositions are filled in plastics containers having oxygen permeability of 3 cc/m2 ·day·atm or more which allow aerobic bacteria to grow or propagate very easily. The use of a polyhydric alcohol in the above-defined contents in combination with an aluminum oxide abrasive renders the toothpaste compositions highly antiseptic. Even when the toothpaste compositions are accidentally contaminated with a substantial amount of bacteria in a plastics container having oxygen permeability of 3 cc/m2 ·day·atm or more, such contamination will be diminished within a relatively short period of time. Since the toothpaste compositions of the present invention are effective to suppress the growth of aerobic bacteria, they may be advantageously stored in plastics containers having a high restoring force for a long period of time without a change in quality. According to the present invention, an antiseptic and/or bactericide may be blended in a minimum amount so that the toothpaste compositions of the present invention are highly safe for oral application.
The above and other objects, features and advantages of this invention will become more apparent and understandable from the following Detailed Description, Examples and Claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 to 3 are partially broken away side views of plastics containers filled with the composition of the present invention, respectively; and
FIG. 4 is a graph showing the relationship between numbers of surviving bacilli and storage period when toothpaste compositions are filled in various containers.
DETAILED DESCRIPTION OF THE INVENTION
The toothpaste composition of this invention comprises an aluminium oxide compound as a main abrasive and a polyhydric alcohol.
The aluminum oxide compounds represented by the general formula:
Al.sub.2 O.sub.3.nH.sub.2 O                                (1)
wherein n≧0, preferably 3≧n≧0, include aluminum oxide when n=0 (that is, an aluminum compound having no water of crystallization and represented by Al2 O3, to be referred to as "alumina", hereinafter) and hydrated aluminum oxides when N>0 (that is, aluminum compounds having water of crystallization, to be referred to as "hydrated aluminas", hereinafter).
Many types of aluminas and hydrated aluminas are known including α, γ, δ, η, θ, κ, χ, ρ and β types classified in terms of crystal systems and physical properties. Among them α-alumina and hydrated α-alumina are preferred because of high stability.
The hydrated aluminas which can be used herein are gibbsite and bayerite (represented by Al2 O3.3H2 O, respectively), boehmite and diaspore (represented by Al2 O3.H2 O, respectively) and the like.
Among these aluminum oxide compounds, hydrated aluminas are preferred in view of abrasiveness, tooth abrasion and the like. Alumina trihydrates having the formula:
Al.sub.2 O.sub.3.3H.sub.2 O or Al(OH).sub.3                (2)
are most preferred because of their mild abrasiveness. The preferred alumina trihydrate is gibbsite which is commercially available.
The aluminum oxide compounds may be used alone or in admixture of two or more.
In view of tooth cleaning and abrasing effects, the aluminum oxide compound should be in the form of particles having an average particle size of 1-50 microns, preferably 3-25 microns when measured by the sedimentation method. The aluminum oxide compound is blended in an amount of 10 to 70% by weight, preferably 30 to 60% by weight of the total weight of the toothpaste composition although the exact blending amount may vary with a particular type of the toothpaste composition.
In addition to the aluminum oxide compound incorporated as the main abrasive as mentioned above, the toothpaste composition of this invention may further include other additional abrasives, for example, dicalcium phosphate dihydrate and anhydride, calcium carbonate, calcium pyrophosphate, silica, aluminum silicate, insoluble sodium metaphosphate, magnesium tertiary phosphate, magnesium carbonate, synthetic resins and other known abrasives alone or in admixture generally in an amount of less than about 10% by weight in terms of the weight of the aluminium oxide compound.
The polyhydric alcohols which can be used in the present invention include ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycerine, sorbitol, xylitol, maltitol, lactitol, etc. and mixtures thereof.
Amounts of the polyhydric alcohols blended fall within the range of 5.0 to 100 moles in fluoride-free systems or within the range of 4.0 to 100 moles in fluoride-containing systems per liter of water in the toothpaste compositions. The presence of polyhydric alcohols in the above-defined ranges is effective to preclude aerobic bacteria from growing or propagating in plastics containers, providing highly antiseptic toothpaste compositions.
In general, the higher the molar number of a polyhydric alcohol, the more effective it is. However, the upper limit of the molar number of a polyhydric alcohol is 100 moles, preferably 50 moles for reasons of toothpaste feeling and cost. More strictly, the upper limit is 15 moles when the smoothness and stringiness of toothpaste upon extrusion are taken into account.
According to the present invention, a fluoride may preferably be blended in the toothpaste composition in addition to the polyhydric alcohol. The fluoride is effective to further improve the antiseptic properties of the toothpaste composition and to lower the lower limit of the amount of the polyhydric alcohols blended as understood from the above-defined ranges. Examples of the fluorides are stannous fluoride, sodium fluoride, and alkali metal monofluorophosphates such as sodium monofluorophosphate, and potassium monofluorophosphate, with the monofluorophosphates being preferred. The fluoride compounds such as alkali metal monofluorophosphates, when blended in an amount of 0.1 to 1% by weight of the total weight of the toothpaste composition, ensure satisfactory antiseptic action and tooth enamel reinforcement.
Preferably, the toothpaste composition of the present invention may further contain as a binder an alkali metal salt of carboxymethyl cellulose such as sodium carboxymethyl cellulose because of the effectiveness to enhance the antiseptic properties of the toothpaste composition. The alkali metal salts of carboxymethyl cellulose may preferably be those having an average degree of etherification of 0.75 to 0.90 because these salts are effective for shape retention of the toothpaste composition. With degrees of etherification of lower than 0.75, the toothpaste compositions become too hard so that an extrudate of toothpaste will readily tumble down from a toothbrush when applied onto the toothbrush. On the other hand, if the average degree of etherification exceeds 0.90, the shape retention of toothpaste becomes lower with repeated squeezing of a plastics container than in the case of an aluminum tube so that an extrudate of toothpaste will undesirably flow on a toothbrush. The carboxymethyl cellulose salts may preferably be blended in an amount of 0.2 to 5%, particularly 0.5 to 2% by weight of the total weight of the toothpaste composition.
The toothpaste composition of the present invention may further contain other additives well know in the art. Examples of such additives include anionic and nonionic surface active agents. The anionic surface active agents may include water-soluble salts of the higher alkyl sulfates having 8 to 18 carbon atoms in the alkyl group (e.g., sodium lauryl sulfate and sodium mirystyl sulfate), water-soluble salts of sulfonated monoglycerides of higher fatty acids having 10 to 18 carbon atoms in the fatty acid group (e.g. sodium lauryl monoglyceride sulfonate and sodium coconut monoglyceride sulfonate), salts of amides of higher fatty acid having 12 to 16 carbon atoms in the fatty acid group with lower aliphatic amino acids (e.g. sodium-N-methyl-N-palmitoyl touride, sodium N-lauroyl sarcosinate, sodium N-methyl glutamate and sodium N-lauroyl- β-alanine), etc. The nonionic surface active agents may include alkyrol diethanol amides (e.g. lauroyl diethanol amide), stearyl monoglyceride, sucrose fatty acid esters having 12 to 18 carbon atoms in the fatty acid group (e.g. sucrose monolaurate and dilaurate), lactose fatty acid esters, lactitol fatty acid esters, maltitol fatty acid esters, condensates of sorbitan monostearate with approximately 60 moles of ethylene oxide, condensates of ethylene oxide with propylene oxide condensates of propylene glycol and their derivatives (e.g. polyoxyethylene polyoxypropylene monolauryl ester), etc. The toothpaste composition may also contain amphoteric surface active agents such as those of betaine and amino acid types, etc. These surface active agents may be blended alone or in admixture in an amount of 0.2 to 7% by weight of the composition.
Also included are flavors such as spearming oil and peppermint oil (in an amount of 0.1 to 3% by weight), clove oil, cassia oil, sage oil, coriander oil, anise oil, wintergreen oil, eucalyptus oil, and fruit flavors (in an amount of 0.001 to 1% by weight). Such a natural essential oil may be partially replaced by a synthetic or isolated flavor, for example, l-menthol, anethole, carvone, eugenol, etc. Furthermore, sweeteners such as sodium saccharin, stevioside, neohesperidin dihydrocalcone, glycyrrhizin, perillartine, p-methoxycinnamic aldehyde, etc. may be blended.
The toothpaste composition of the present invention may contain humectants other than polyhydric alcohols as well as binders other than alkali metal salts of carboxymethyl cellulose. Examples of the other binders include carrageenan, alkali metal alginates such as sodium alginate, gums such as xanthan gum, synthetic binding agents such as polyvinyl alcohol, inorganic binding agents such as silica gel, veegum, aluminum silicate gel, etc. and mixtures thereof. The other binders may be blended alone or in admixture, preferably in admixture with alkali metal salts of carboxymethyl cellulose in an amount of 0 to 2% by weight of the composition.
In addition to fluorides, the toothpaste composition of this invention may further include other active ingredients, for example, enzymes such as amylase, protease, mutanase, lysozyme, lytic enzyme, etc., stannous compounds, ε-aminocaproic acid, tranexamic acid, aluminum chlorohydroxyallantoinate, dihydrocholesterol, glycyrrhetinates, glycerophosphate, sodium chloride, water-soluble inorganic phosphates, and the like alone or in admixture. Examples of the watersoluble inorganic phosphate are potassium and sodium salts of orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid, while the potassium salts are preferred.
In the toothpaste composition, antiseptics such as ethyl p-hydroxybenzoate and butyl p-hydroxybenzoate, and bactericides such as bacterial quarternary ammonium salts and chlorhexidine and its salts may be blended in an amount of 0 to 0.5% by weight of the composition.
Other well-known ingredients may also be blended in the composition.
The toothpaste composition of the present invention may be prepared by selecting the necessary ingredients from the above-mentioned ingredients and kneading them with water.
The toothpaste composition according to this invention may generally have a pH or 4.5 to 10, preferably 6 to 8.5.
The thus prepared toothpaste composition is packed into a plastics container including a plastics tube formed solely of plastics material, an aluminum foil-plastics coating laminate tube which comprises an aluminum foil coated with a plastics layer on an inner or each surface and formed into a tube, and a plastic bottle. FIG. 1 shows one example of a collapsable plastics tube. The tube 10 has a tubular body 12 which consists of a plastics material inner layer 14 and a plastic material outer layer 16, a shoulder 18, and a cap 20. FIG. 2 shows one example of a collapsable laminate tube. The tube 24 has a tubular body 26 which consists of a plastics material inner layer 28, an aluminum foil intermediate layer 30 and a plastics material outer surface 32, a shoulder 34, and a cap 36. FIG. 3 shows one example of a plastic bottle. The bottle 40 has a bottle body 42 which consists of a plastic material single layer 44, and a cap 46. In FIGS. 1 to 3, numerals 22, 38 and 48 designate a toothpaste composition packed in the containers 10, 24 and 40. The number of the layer(s) is not limited to the above Figures. The body of the plastics container may have a single layer or multiple layers. Plastic material of the plastic containers may be selected from ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyvinyl chloride, nylon, polyester, polyethylene, polypropylene, etc. The toothpaste composition of the present invention is advantageously and safely stored in the plastics container having oxygen permeability of 3 cc/m2 ·day·atm or more for a long period of time without a change in quality because they are effective to prevent aerobic bacteria from growing or propagating. More detailedly, a plastics container having oxgen permeability of 3 cc/m2 ·day·atm or more would allow aerobic bacteria to grow or propagate very easily in its content or toothpaste compositions. However, when the toothpaste compositions according to the present invention are filled in the plastic container having oxgen permeability of 3 cc/m2 ·day·atm or more, aerobic bacteria are effectively prevented from growing or propagating because the antiseptic properties of the toothpaste composition according to the present invention are very high.
The following examples are illustrative of this invention. However, it is to be understood that the invention is not limited to the examples. All percents are by weight.
EXAMPLE 1
Toothpaste compositions having the formulation shown below were prepared in a conventional manner.
______________________________________                                    
Ingredients (% by weight)                                                 
______________________________________                                    
Dicalcium phosphate dihydrate                                             
                         55%                                              
Propylene glycol        2.5                                               
Sorbitol                16                                                
Sodium carboxymethyl cellulose                                            
                        0.6                                               
(average etherification degree 0.78)                                      
Carrageenan             0.4                                               
Sodium saccharin         0.15                                             
Sodium lauryl sulfate   1.5                                               
Flavor                  1.0                                               
Water                   23.35                                             
Total                   100.0%                                            
Total mole number of polyhydric alcohols                                  
                         4.89                                             
(mol/l of water)                                                          
______________________________________
The toothpaste samples were filled in the following tubes A-H, respectively.
Tube A: Laminate tube having an epoxy resin inner layer of 20 μm thick, an aluminum foil intermediate layer of 10 μm thick and a low-density polyethylene outer layer of 100 μm thick. The shoulder portion of the tube A consists of a polyethylene single layer.
Tube B: Laminate tube having an epbxy resin inner layer of 20 μm thick, an aluminum foil intermediate layer of 15 μm thick and a low-density polyethylene outer layer of 100 μm thick. The shoulder portion of the tube B consists of a polyethylene single layer.
Tube C: Laminate tube having an epoxy resin inner layer of 20 μm thick, an aluminum foil intermediate layer of 20 μm thick and a low-density polyethylene outer layer of 100 μm thick. The shoulder portion of the tube C consists of inner and outer layers of polyethylene and an intermediate layer of aluminum foil.
Tube D: Laminate tube having an epoxy resin inner layer of 20 μm thick, an aluminum foil intermediate layer of 20 μm thick and a low-density polyethylene outer layer of 100 μm thick. The shoulder portion of the tube D consists of an inner layer of urea resin and an outer layer of polyethylene.
Tube E: Plastics tube having an ethylene-vinyl acetate copolymer inner layer (vinyl acetate content 10%) of 200 μm thick, an ethylenevinyl alcohol intermediate layer of 50 μm thick and an ethylene-vinyl acetate copolymer inner layer of 250 μm thick.
Tube F: Plastics tube having a single layer of 500 μm which consists of a mixture of 100 parts by weight of a blend of 20% of a low-density polyethylene (density 0.917) with 80% of a saponified ethylene-vinyl acetate copolymer (ethylene content 76%, degree of saponification 93%) and 5 parts by weight of a polyamide having a carbonyl concentration of 1.6 meq./g.
Tube G: Plastics tube having an inner layer of 350 μm thick which consists of a blend of 55% of a low-density polyethylene (density 0.917) with 45% of a saponified ethylene-vinyl acetate copolymer (ethylene content 76%, degree of saponification 93%) and an outer layer of 150 μm thick which consists of a polyamide having a carbonyl concentration of 1.6 meq./g.
Tube H: Aluminum tube
Oxygen permeability (cc/m2 ·day·atm) of the tubes A-H was measured by the following method. The results are shown in Table 1.
A tube to be measured is evacuated and purged with nitrogen gas, closed at its opening with a rubber plug, and sealed at the interface between the tube opening and the plug with an epoxy adhesive. The tube is then kept for a given period of time in a temperature and humidity-controlled chamber at a temperature of 37° C. and a relative humidity of 15%. The concentration of oxygen which has permeated through the tube wall into the tube interior is measured by gas chromatography, and the oxygen permeability QO2 is calculated according to the following equation: ##EQU1## Where m is the volume in ml of nitrogen gas with which the tube is filled, t is the time in day for which the tube is kept in the chamber, Ct is the concentration in vol. % of oxygen in the tube after t days, A is the effective surface area in m2 of the tube, and Op is the partial pressure of oxygen gas which is equal to 0.209 atm. The result is an average of three tube samples.
              TABLE 1                                                     
______________________________________                                    
Tube     O.sub.2 permeability (cc/m.sup.2 · day ·       
______________________________________                                    
         atm)                                                             
A        9                                                                
B        3                                                                
C          3.3                                                            
D        <3                                                               
E        <3                                                               
F        245                                                              
G        45                                                               
H        <3                                                               
______________________________________
The toothpaste samples filled in the above tubes were tested for antiseptic properties by the following method. Gram-negative bacillus was isolated from the environment and stored in a slant. A trypticase soy plateoculture medium was smeared with the bacillus. After cultivation at 32° C. for 48 hours, the bacillus which had grown on the plate was scraped and suspended in a sterilized physiological saline solution to form a thick bacillus suspension. The toothpaste samples were inoculated with the above-prepared bacillus suspension to a concentration of 106 -107 bacillus/g of toothpaste and thoroughly kneaded. Laminate tubes formed of an aluminum foil coated with a polyethylene film on each surface were filled with the contaminated toothpaste samples and stored at 30° C. The number of surviving bacilli in the toothpaste samples was determined after 1, 2 and 4 weeks. The results are shown in FIG. 4.
The evaluation standard is as follows.
______________________________________                                    
Number of surviving bacilli                                               
______________________________________                                    
           ++:  ≧10.sup.5 /g                                       
           +:   10.sup.3 -10.sup.5 /g                                     
           ±:                                                          
                about 10.sup.2 /g                                         
           -:   ≦10/g                                              
______________________________________
As seen from FIG. 4, the toothpaste compositions filled in the plastics containers having oxygen permability of 3 cc/m2 ·day·atm or more are not antiseptic. In other words, it was found that plastics containers having oxygen permeability of 3 cc/m2 ·day·atm or more allow aerobic bacteria to grow or propagate very easily as compared with the other tubes having oxygen permeability of less than 3 cc/m2 ·day·atm.
EXAMPLE 2
Twelve toothpaste compositions each having the formulation shown in Table 2 were prepared in a conventional manner.
                                  TABLE 2                                 
__________________________________________________________________________
               SAMPLE NO.                                                 
Ingredients (% by weight)                                                 
               1   2   3   4   5   6   7   8   9   10  11  12             
__________________________________________________________________________
Dicalcium phosphate dihydrate                                             
               52.0%                                                      
                   49.6%                                                  
                       46.9%           52.0%                              
                                           49.6%                          
                                               46.9%                      
Alumina trihydrate (gibbsite,                                             
                           52.0%                                          
                               49.6%                                      
                                   46.9%           52.0%                  
                                                       49.6%              
                                                           46.9%          
average particle size 9                                                   
microns)                                                                  
Propylene glycol                                                          
               2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5            
Sorbitol       15.0                                                       
                   18.0                                                   
                       21.0                                               
                           15.0                                           
                               18.0                                       
                                   21.0                                   
                                       12.0                               
                                           15.0                           
                                               18.0                       
                                                   12.0                   
                                                       15.0               
                                                           18.0           
Sodium carboxymethyl                                                      
               0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6            
cellulose (average etherifica-                                            
tion degree 0.78)                                                         
Carrageenan    0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4            
Sodium saccharin                                                          
               0.15                                                       
                   0.15                                                   
                       0.15                                               
                           0.15                                           
                               0.15                                       
                                   0.15                                   
                                       0.15                               
                                           0.15                           
                                               0.15                       
                                                   0.15                   
                                                       0.15               
                                                           0.15           
Sodium lauryl sulfate                                                     
               1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5            
Flavor         1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0            
Sodium monoflourophosphate                                                
               0   0   0   0   0   0   0.76                               
                                           0.76                           
                                               0.76                       
                                                   0.76                   
                                                       0.76               
                                                           0.76           
Water          26.85                                                      
                   26.25                                                  
                       25.95                                              
                           26.85                                          
                               26.25                                      
                                   25.95                                  
                                       29.09                              
                                           28.49                          
                                               28.19                      
                                                   20.09                  
                                                       28.49              
                                                           28.19          
Total          100.0                                                      
                   100.0                                                  
                       100.0                                              
                           100.0                                          
                               100.0                                      
                                   100.0                                  
                                       100.0                              
                                           100.0                          
                                               100.0                      
                                                   100.0                  
                                                       100.0              
                                                           100.0          
Total mole number of poly-                                                
               4.3 5.0 5.7 4.3 5.0 5.7 3.4 4.0 4.7 3.4 4.0 4.7            
hydric alcohols (mol/l of                                                 
water)                                                                    
__________________________________________________________________________
In Table 2, samples Nos. 5,6,11 and 12 fall within the scope of the present invention and other samples are shown for the purpose of comparison.
These samples were filled in the tubes A shown in Example 1 and were tested for antiseptic properties by the same method as in Example 1. The results are shown in Table 3.
                                  TABLE 3                                 
__________________________________________________________________________
Sample                                                                    
    Molar number of      Sodium mono-                                     
                                 Storage period                           
No. polyhydric alcohol                                                    
              Abrasive   fluorophosphate                                  
                                 1 week                                   
                                     2 weeks                              
                                          1 month                         
__________________________________________________________________________
1   4.3       Dicalcium phosphate                                         
                         0       ++  ++   ++                              
2   5.0       "          0       ++  ++   ++                              
3   5.7       "          0       ++  ++   ++                              
4   4.3       Alumina trihydrate                                          
                         0       ++  ++   ++                              
5   5.0       "          0       ±                                     
                                     -    -                               
6   5.7       "          0       -   -    -                               
7   3.4       Dicalcium phosphate                                         
                         0.76%   ++  ++   ++                              
8   4.0       "          0.76%   ++  ++   ++                              
9   4.7       "          0.76%   ++  ++   ++                              
10  3.4       Alumina trihydrate                                          
                         0.76%   ++  ++   ++                              
11  4.0       "          0.76%   ±                                     
                                     -    -                               
12  4.7       "          0.76%   -   -    -                               
__________________________________________________________________________
As seen from the data of Table 3, satisfactorily antiseptic toothpaste compositions are obtained using alumina abrasive in combination with at least 5.0 moles of a polyhydric alcohol in fluoride-free systems or at least 4.0 moles of a polyhydric alcohol in fluoride-containing systems.
Aluminum tubes and laminate tubes formed of an aluminum foil having a polyethylene coating on each surface were filled with toothpaste sample Nos. 1 to 6. After being stored at room temperature and 50° C. for one month, the samples were measured for stability. All the toothpaste samples themselves were found to be satisfactorily stable. However, corrosion and blister were observed in those aluminum tubes filled with toothpaste sample Nos. 4 to 6 containing alumina trihydrate abrasive. No problem occurred in the laminate tubes filled with the same samples. Neither the aluminum tubes nor the laminate tubes gave rise to any problem when they were filled with toothpaste sample Nos. 1 to 3 containing dicalcium phosphate abrasive.
______________________________________                                    
                   % by weight                                            
______________________________________                                    
Alumina trihydrate (Al.sub.2 O.sub.3.3H.sub.2 O,                          
                     45                                                   
gibbsite, average particle                                                
size 10μ)                                                              
Glycerine            15                                                   
                             (8.3 moles/l)                                
Sorbitol             10                                                   
Sodium carboxymethyl cellulose                                            
                     1.0                                                  
(average degree of etherifi-                                              
cation 0.85)                                                              
Sodium saccharin     0.1                                                  
Sodium lauryl sulfate                                                     
                     1.5                                                  
Flavor (peppermint type)                                                  
                     1.0                                                  
Water                26.4                                                 
                     100.0%                                               
______________________________________
A plastics tube having oxygen permeability of 25 cc/m2 ·day·atm was filled with the above composition.
EXAMPLE 4 
______________________________________                                    
                   % by weight                                            
______________________________________                                    
Alumina trihydrate (Al.sub.2 O.sub.3.3H.sub.2 O,                          
                     27                                                   
average particle size 15μ)                                             
Silica               3                                                    
Sorbitol             33      (5.5 moles/l)                                
Sodium carboxymethyl cellulose                                            
                     0.5                                                  
(average degree of etherifi-                                              
cation 0.77)                                                              
Carrageenan          0.5                                                  
Sodium saccharin     0.1                                                  
Sodium lauryl sulfate                                                     
                     2.0                                                  
Flavor (spearmint type)                                                   
                     1.0                                                  
Water                32.9                                                 
                     100.0%                                               
______________________________________
A plastics tube having oxygen permeability of 8 cc/m2 ·day·atm was filled with the above composition.
EXAMPLE 5 
______________________________________                                    
                    % by weight                                           
______________________________________                                    
Alumina trihydrate (Al.sub.2 O.sub.3.3H.sub.2 O,                          
                     55                                                   
gibbsite, average particle                                                
size 9μ)                                                               
Propylene glycol     2                                                    
                             (4.6 moles/l)                                
Sorbitol             14                                                   
Sodium alginate      0.5                                                  
Carrageenan          0.5                                                  
Gelatin              0.5                                                  
Sodium saccharin     0.1                                                  
Sodium monofluorophosphate                                                
                     0.76                                                 
Lauroyl diethanol amide                                                   
                     1.5                                                  
Sodium lauryl sulfate                                                     
                     1.5                                                  
Flavor               1.0                                                  
Water                22.64                                                
                     100.0%                                               
______________________________________
A laminate tube formed of an aluminum foil having a plastics coating on each surface was filled with the above composition. The laminate tube had oxygen permeability of 5 cc/m2 ·day·atm. The flavor used in the above composition was a mixture of the following components:
______________________________________                                    
l-menthol         0.3    parts by weight                                  
carvone           0.05   "                                                
anethole          0.1    "                                                
peppermint oil    0.5    "                                                
spearmint oil     0.05   "                                                
______________________________________
EXAMPLE 6 
______________________________________                                    
                    % by weight                                           
______________________________________                                    
Alumina hydrate (Al.sub.2 O.sub.3.H.sub.2 O,                              
                     50.0                                                 
boehmite, average particle                                                
size 20μ)                                                              
Propylene glycol     3.0                                                  
Glycerine            12.0    (7.3 moles/l)                                
Sorbitol             5.0                                                  
Sodium carboxymethyl cellulose                                            
                     1.0                                                  
(average degree of etherification 0.8)                                    
Carrageenan          0.2                                                  
Sodium saccharin     0.1                                                  
Sodium lauryl sulfate                                                     
                     1.0                                                  
Flavor (double mint type)                                                 
                     0.8                                                  
Water                26.9                                                 
                     100.0%                                               
______________________________________
A plastics tube having oxygen permeability of 120 cc/m2 ·day·atm was filled with the above composition.
EXAMPLE 7 
______________________________________                                    
                     % by weight                                          
______________________________________                                    
Alpha-alumina (average particle                                           
                      15                                                  
size 3μ)                                                               
Glycerine             50                                                  
                              (28.6 moles/l)                              
Sorbitol              10                                                  
Sodium carboxymethyl cellulose (average                                   
                      1.0                                                 
degree of etherification 0.88)                                            
Sodium saccharin      0.1                                                 
Sodium lauryl sulfate 2.0                                                 
Flavor (peppermint type)                                                  
                      1.0                                                 
Water                 20.9                                                
                      100.0%                                              
______________________________________
A plastic tube having oxygen permeability of 72 cc/m2 ·day·atm was filled with the above composition.
EXAMPLE 8 
______________________________________                                    
                    % by weight                                           
______________________________________                                    
Alpha-alumina        56                                                   
Propylene glycol     2                                                    
                             (5.3 moles/l)                                
Sorbitol             16                                                   
Sodium carboxymethyl cellulose                                            
                     1.0                                                  
Sodium saccharin     0.1                                                  
Sodium fluoride      0.22                                                 
Sodium lauryl sulfate                                                     
                     2.0                                                  
Flavor (spearmint type)                                                   
                     1.0                                                  
Water                21.68                                                
                     100.0%                                               
______________________________________
A laminate tube formed of an aluminum foil having a plastics coating on each surface was filled with the above composition. The laminate tube had oxygen permeability of 9 cc/m2 ·day·atm.
EXAMPLE 9 
______________________________________                                    
                    % by weight                                           
______________________________________                                    
Alumina hydrate (Al.sub.2 O.sub.3.H.sub.2 O,                              
                     50                                                   
boehmite, average particle                                                
size 20μ)                                                              
Propylene glycol     3                                                    
Glycerine            12      (7.5 moles/l)                                
Sorbitol             5                                                    
Stannous fluoride    0.41                                                 
Sodium carboxymethyl cellulose                                            
                     1.5                                                  
Sodium saccharin     0.1                                                  
Sodium lauryl sulfate                                                     
                     1.0                                                  
Flavor (spearmint type)                                                   
                     0.5                                                  
Water                26.49                                                
                     100.0%                                               
______________________________________
A laminate tube formed of an aluminum foil having a plastics coating on each surface was filled with the above composition. The laminate tube had oxygen permeability of 12 cc/m2 ·day·atm.

Claims (20)

What is claimed is:
1. A toothpaste composition with which a plastics container having oxygen permeability of 3 cc/m3·day·atm or more is filled, characterized in that the toothpaste composition comprises an aluminum oxide compound as a main abrasive, water, a polyhydric alcohol in an amount of 5.0 to 100 moles per liter of water in the toothpaste composition, and a binder, wherein said toothpaste composition exhibits antiseptic action against aerobic bacteria.
2. A toothpaste composition according to claim 1 wherein the aluminum oxide compound is present in an amount of 10 to 70% by weight of the total weight of the composition.
3. A toothpaste composition according to claim 1 wherein the aluminum oxide compound has the fomula:
Al.sub.2 O.sub.3 ·nH.sub.2 O
wherein n has a value ranging from 0 to 3.
4. A toothpaste composition according to claim 3 wherein the aluminum oxide compound is aluminum oxide trihydrate.
5. A toothpaste composition according to claim 1 wherein the polyhydric alcohol is present in an amount of 5.0 to 15 moles per liter of water in the toothpaste composition.
6. A toothpaste composition according to claim 1 wherein the polyhydric alcohol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycerine, xylitol, maltitol, lactitol and sorbitol, and mixtures thereof.
7. A toothpaste composition according to claim 1 wherein the binder comprises an alkali metal salt of carboxymethyl cellulose having an average degree of etherification of 0.75 to 0.90 in an amount of 0.2 to 5% by weight of the total weight of the toothpaste composition.
8. A toothpaste composition according to claim 1 wherein the plastics container is selected from the group consisting of a plastic tube formed solely of plastics material, a laminate tube comprising an aluminium foil coated with a plastics layer on an inner or each surface and formed into a tube, and a plastic bottle.
9. A toothpaste composition according to claim 1 wherein the pH of the toothpaste composition is 4.5 to 10.
10. A toothpaste composition with which a plastics container having oxygen permeability of 3 cc/m2 ·day·atm or more is filled, characterized in that the toothpaste composition comprises an aluminum oxide compound as a main abrasive, water, a polyhydric alcohol in an amount of 4.0 to 100 moles per liter of water in the toothpaste composition, a fluoride, and a binder, wherein said toothpaste composition exhibits antiseptic action against aerobic bacteria.
11. A toothpaste composition according to claim 10 wherein the fluoride is an alkali metal monofluorophosphate.
12. A toothpaste composition according to claim 11 wherein the alkali metal monofluorophosphate is present in an amount of 0.1 to 1% by weight of the total weight of the composition.
13. A toothpaste composition according to claim 10 wherein the aluminum oxide compound is present in an amount of 10 to 70% by weight of the total weight of the composition.
14. A toothpaste composition according to claim 10 wherein the aluminum oxide compound has the formula:
Al.sub.2 O.sub.3.nH.sub.2 O
wherein n has a value ranging from 1 to 3.
15. A toothpaste composition according to claim 14 wherein the aluminum oxide compound is aluminum oxide trihydrate.
16. A toothpaste composition according to claim 10 wherein the polyhydric alcohol is present in an amount of 4.0 to 15 moles per liter of water in the toothpaste composition.
17. A toothpaste composition according to claim 10 wherein the polyhydric alcohol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycerine, xylitol, maltitol, lactitol and sorbitol, and mixtures thereof.
18. A toothpaste composition according to claim 10 wherein the binder comprises an alkali metal salt of carboxymethyl cellulose having an average degree of etherification of 0.75 to 0.90 in an amount of 0.2 to 5% by weight of the total weight of the toothpaste composition.
19. A toothpaste composition according to claim 10 wherein the plastics container is selected from the group consisting of a plastic tube formed solely of plastics material, a laminate tube comprising an aluminium foil coated with a plastics layer on an inner or each surface and formed into a tube, and a plastic bottle.
20. A toothpaste composition according to claim 10 wherein the pH of the toothpaste composition is 4.5 to 10.
US06/499,447 1980-11-20 1983-05-31 Toothpaste composition Expired - Fee Related US4556553A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP55-163739 1980-11-20
JP55163739A JPS5788112A (en) 1980-11-20 1980-11-20 Tooth-paste composition

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US06/316,400 Continuation-In-Part US4581228A (en) 1980-11-20 1981-10-29 Toothpaste composition and plastic containers containing the same

Publications (1)

Publication Number Publication Date
US4556553A true US4556553A (en) 1985-12-03

Family

ID=15779750

Family Applications (2)

Application Number Title Priority Date Filing Date
US06/316,400 Expired - Fee Related US4581228A (en) 1980-11-20 1981-10-29 Toothpaste composition and plastic containers containing the same
US06/499,447 Expired - Fee Related US4556553A (en) 1980-11-20 1983-05-31 Toothpaste composition

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US06/316,400 Expired - Fee Related US4581228A (en) 1980-11-20 1981-10-29 Toothpaste composition and plastic containers containing the same

Country Status (2)

Country Link
US (2) US4581228A (en)
JP (1) JPS5788112A (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4702905A (en) * 1985-08-30 1987-10-27 Colgate-Palmolive Company Packaged dental cream
US4716034A (en) * 1985-11-27 1987-12-29 Colgate-Palmolive Company Packaged dental cream
US4728508A (en) * 1985-12-13 1988-03-01 Colgate-Palmolive Company Dental cream in package
EP0304327A3 (en) * 1987-08-21 1989-05-31 Unilever Plc Toothpastes
US5041279A (en) * 1986-02-28 1991-08-20 Colgate-Palmolive Company Dental cream package
WO2000037034A1 (en) * 1998-12-18 2000-06-29 Colgate-Palmolive Company Polyolefin packaged dentrifrice having reduced flavor loss
DE19925097A1 (en) * 1999-06-01 2000-12-07 Henco Ind Nv Herentals Composite pipe manufacturing process to reduce water and oxygen permeability uses an inner layer of PVDC and an outer layer of another plastic
US6174515B1 (en) 2000-06-05 2001-01-16 Amway Corporation Toothpaste composition
US6238648B1 (en) * 1999-03-25 2001-05-29 The Procter & Gamble Company Anti-caries oral care compositions and their methods of use
US20050025720A1 (en) * 2003-06-20 2005-02-03 Donald W. Bailey Xylitol dental maintenance system
US20050089481A1 (en) * 2003-10-23 2005-04-28 Gc Corporation Composition for caries prevention
KR100517448B1 (en) * 1997-11-28 2005-11-28 헤르큘레스 인코포레이티드 Dispersible water-soluble or water-swellable polymers and process for making toothpastes containing them
US20100158820A1 (en) * 2003-06-20 2010-06-24 Bailey Donald W Xylitol dental maintenance system
US20160067171A1 (en) * 2013-05-28 2016-03-10 Henkel Ag & Co. Kgaa Oral and dental hygiene and cleaning agents with optimized taste
US20220054372A1 (en) * 2020-08-24 2022-02-24 The Procter & Gamble Company Tooth whitening product

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4247116B2 (en) * 2001-10-25 2009-04-02 花王株式会社 Dentifrice
US20030175337A1 (en) * 2001-10-29 2003-09-18 Franz G. Andrew Levothyroxine compositions having unique triiodothyronine Tmax properties
US7578256B2 (en) * 2004-12-03 2009-08-25 Matthew Daley Bookmark

Family Cites Families (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2010910A (en) * 1932-05-04 1935-08-13 Malcolm W Atkins Dental cleaning and polishing compound
US2136033A (en) * 1936-10-26 1938-11-08 Surgident Ltd Dispensing package of thermoplastic material
US2550207A (en) * 1949-01-25 1951-04-24 Sterling Drug Inc Dentifrice compositions
US2671996A (en) * 1949-10-22 1954-03-16 Colgate Palmolive Co Packaging of materials
US2671995A (en) * 1949-10-22 1954-03-16 Colgate Palmolive Co Packaging of materials
US2818371A (en) * 1953-10-26 1957-12-31 Sterling Drug Inc Fluoride-containing dentifrices
US3060098A (en) * 1957-11-18 1962-10-23 Lever Brothers Ltd Dentifrice
US2984570A (en) * 1959-04-23 1961-05-16 Sarah A Prell Dispenser container and method of altering the flavor and color of a substance packaged therein
US3115248A (en) * 1959-10-14 1963-12-24 Colgate Palmolive Co Packaging of materials and means therefor
US3295725A (en) * 1962-12-07 1967-01-03 American Can Co Collapsible dispensing container with an impermeable barrier both in its laminated wall and in its headpiece
US3182795A (en) * 1963-03-01 1965-05-11 Olin Mathieson Container for toothpaste containing stannous fluoride and process for reducing corrosion thereof
US3160323A (en) * 1963-04-05 1964-12-08 Leonard R Weisberg Containers with internal, interlocking protrusions
GB1054004A (en) * 1964-05-05
US3313455A (en) * 1965-06-18 1967-04-11 Nicholas J Kemmer Collapsible tube squeezing device
US3505143A (en) * 1966-03-10 1970-04-07 American Can Co Method of laminating sheet material by coating metal foil with a copolymer of ethylene and an ethylenically unsaturated carboxylic acid
US4168301A (en) * 1967-03-03 1979-09-18 Lever Brothers Company Dentifrice based on high particle size alpha-alumina trihydrate
NL157268C (en) * 1968-03-20
AT280481B (en) * 1968-07-01 1970-04-10 Blendax Werke Schneider Co Dental and oral hygiene preparations containing water
ZA695572B (en) * 1968-08-09 1971-03-31 Colgate Palmolive Co Oral preparation
GB1277586A (en) * 1968-10-29 1972-06-14 Unilever Ltd Toothpastes
US4150113A (en) * 1969-06-03 1979-04-17 Telec S.A. Enzymatic dentifrices
US3599837A (en) * 1969-06-06 1971-08-17 Dave Chapman Goldsmith & Yamos Plastic dispensing container and closure therefor
BE756129A (en) * 1969-09-25 1971-02-15 Blendax Werke Schneider Co DENTRIFICE PRODUCT
US3622661A (en) * 1970-07-13 1971-11-23 Colgate Palmolive Co Oral preparations
ZA714595B (en) * 1970-08-05 1973-02-28 Colgate Palmolive Co Plastic package of materials
GB1373003A (en) * 1971-01-28 1974-11-06 Unilever Ltd Dentifrice composition
JPS4886043U (en) * 1972-01-18 1973-10-18
US4011968A (en) * 1973-08-31 1977-03-15 Colgate-Palmolive Company Collapsible containers
GB1491211A (en) * 1974-03-07 1977-11-09 Unilever Ltd Process for inhibiting the swelling of aluminium toothpaste tubes
US4098878A (en) * 1974-10-29 1978-07-04 Colgate-Palmolive Company Toothpaste containing milled alpha-alumina trihydrate
JPS5166078A (en) * 1974-12-03 1976-06-08 Sunstar Inc PURASUCHITSUKUSEKI SOOSHIDA SHICHUUBU
GB1475252A (en) * 1975-01-15 1977-06-01 Colgate Palmolive Co Toothpaste composition
CA1043264A (en) * 1975-03-25 1978-11-28 Martin Cordon Dentifrices
US4196825A (en) * 1975-09-08 1980-04-08 Colgate-Palmolive Company Laminated collapsible tube
JPS5254037A (en) * 1975-10-28 1977-05-02 Sunstar Inc Lysozymeeblended dentifrice composition
US4118471A (en) * 1977-06-09 1978-10-03 Colgate-Palmolive Company Stable dentifrice
US4142630A (en) * 1977-11-07 1979-03-06 Ethyl Corporation Collapsible dispensing tube
US4265948A (en) * 1977-11-07 1981-05-05 Ethyl Corporation Collapsible dispensing tube
DE2852124A1 (en) * 1977-12-07 1979-06-13 Unilever Nv TOOTHPASTE
JPS54147939A (en) * 1978-05-08 1979-11-19 Sunstar Inc Tooth polishing composition
US4269822A (en) * 1979-07-20 1981-05-26 Laclede Professional Products, Inc. Antiseptic dentifrice

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4702905A (en) * 1985-08-30 1987-10-27 Colgate-Palmolive Company Packaged dental cream
US4716034A (en) * 1985-11-27 1987-12-29 Colgate-Palmolive Company Packaged dental cream
US4728508A (en) * 1985-12-13 1988-03-01 Colgate-Palmolive Company Dental cream in package
US5041279A (en) * 1986-02-28 1991-08-20 Colgate-Palmolive Company Dental cream package
EP0304327A3 (en) * 1987-08-21 1989-05-31 Unilever Plc Toothpastes
EP0304325A3 (en) * 1987-08-21 1989-05-31 Unilever Plc Toothpastes
US4927625A (en) * 1987-08-21 1990-05-22 Lever Brothers Company Toothpastes
US4935227A (en) * 1987-08-21 1990-06-19 Lever Brothers Company Toothpastes
US4935226A (en) * 1987-08-21 1990-06-19 Lever Brothers Co. Toothpastes
KR100517448B1 (en) * 1997-11-28 2005-11-28 헤르큘레스 인코포레이티드 Dispersible water-soluble or water-swellable polymers and process for making toothpastes containing them
WO2000037034A1 (en) * 1998-12-18 2000-06-29 Colgate-Palmolive Company Polyolefin packaged dentrifrice having reduced flavor loss
US6238648B1 (en) * 1999-03-25 2001-05-29 The Procter & Gamble Company Anti-caries oral care compositions and their methods of use
DE19925097A1 (en) * 1999-06-01 2000-12-07 Henco Ind Nv Herentals Composite pipe manufacturing process to reduce water and oxygen permeability uses an inner layer of PVDC and an outer layer of another plastic
DE19925097B4 (en) * 1999-06-01 2006-03-09 Henco Industries Nv Composite tube with PVDC inner layer
US6174515B1 (en) 2000-06-05 2001-01-16 Amway Corporation Toothpaste composition
US20050025720A1 (en) * 2003-06-20 2005-02-03 Donald W. Bailey Xylitol dental maintenance system
US20100158820A1 (en) * 2003-06-20 2010-06-24 Bailey Donald W Xylitol dental maintenance system
US8524198B2 (en) 2003-06-20 2013-09-03 Donald W. Bailey Xylitol dental maintenance system
US20050089481A1 (en) * 2003-10-23 2005-04-28 Gc Corporation Composition for caries prevention
US20160067171A1 (en) * 2013-05-28 2016-03-10 Henkel Ag & Co. Kgaa Oral and dental hygiene and cleaning agents with optimized taste
US20220054372A1 (en) * 2020-08-24 2022-02-24 The Procter & Gamble Company Tooth whitening product
CN116157272A (en) * 2020-08-24 2023-05-23 宝洁公司 Tooth whitening product

Also Published As

Publication number Publication date
US4581228A (en) 1986-04-08
JPS5788112A (en) 1982-06-01
JPH021124B2 (en) 1990-01-10

Similar Documents

Publication Publication Date Title
US4556553A (en) Toothpaste composition
US4923684A (en) Tripolyphosphate-containing anti-calculus toothpaste
US5882631A (en) Oral composition
US4985236A (en) Tripolyphosphate-containing anti-calculus toothpaste
US4562066A (en) Astringent dentifrice containing monofluorophosphate
US5820852A (en) Oral compositions containing fluoride, pyrophosphate, and peroxide
US4469673A (en) Oral composition
JPS6234013B2 (en)
US4383987A (en) Foaming dentifrice containing nonionic surface active agent
US4576816A (en) Dentifrice composition
US4816245A (en) Antiplaque/antigingivitis method using certain polyphosphonic acids
SE413223B (en) MUNHYGIA COMPOSITION INCLUDING A CALCIUM CARBONATE SLIP, A IONIC FLUORIDE AND A IONIC MONOFLUOROPHOSPHATE
CA2300676A1 (en) Oral compositions
US4562065A (en) Astringent dentifrice
EP0397452B1 (en) Anti-calculus toothpaste compositions having improved shelf-life
US4716034A (en) Packaged dental cream
US4407788A (en) Dentifrice
JPH04139120A (en) Composition for use in oral cavity
US4562063A (en) Astringent gel dentifrice
US4770324A (en) Dental cream package
FI87732C (en) FOERPACKAD TANDKRAEM
JPS63192712A (en) Toothpaste
EP0708635B1 (en) Oral effervescent compositions
JPS6075412A (en) Dentifrice composition
JP3315733B2 (en) Oral composition

Legal Events

Date Code Title Description
AS Assignment

Owner name: LION CORPORATION, NO. 3-7, 1-CHOME, HONJO, SUMIDA-

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:SUGANUMA, NOBUO;TANAKA, KENSUKE;TAKADA, NOBUYUKI;AND OTHERS;REEL/FRAME:004146/0230

Effective date: 19830617

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19971203

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362